US3410910A - Catalytic process for preparing unsaturated aldehydes - Google Patents

Catalytic process for preparing unsaturated aldehydes Download PDF

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US3410910A
US3410910A US319534A US31953463A US3410910A US 3410910 A US3410910 A US 3410910A US 319534 A US319534 A US 319534A US 31953463 A US31953463 A US 31953463A US 3410910 A US3410910 A US 3410910A
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catalyst
propylene
reaction
acid
solution
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US319534A
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Giordano Nicola
Caporali Giorgio
Ferlazzo Natale
Roberti Lamberto
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Montedison SpA
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Montedison SpA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene

Definitions

  • This invention relates to the preparation of unsaturated aliphatic aldehydes.
  • a p ocess for the production of unsaturated aliphatic aldehydes which includes reacting an olefinic hydrocarbon in the gaseous phase with oxygen, or a gas containing oxygen, in the presence of a catalyst which comprises a heter-opoly compound obtained by reacting at least one heteropolyacid having as a co-ordinating element a rare-earth element of either the actinide or the lanthanide series and including as a co-ordinated element at least one of the elements tungsten, molybdenum and vanadium, or an ammonium salt of such an acid, with a salifying compound containing bismuth or tellurium.
  • Heteropolyacids are considered as resulting from two or more molecules of two or more different acids by elimination of water molecules (heterodiacids, heterotriacids, heterotetraacids). More particularly they may be considered as resulting from the union of a definite number of molecules of acid anhydrides, defined as the co-ordinated elements, with molecules of a second acid that supplies the central atom (defined as the co-ordinating element) of the polyanionic complex.
  • A is cerium or thorium; and D is tungsten or molybdenum;
  • ceric-IO-molybdo-Z-vanadic acid H CeM0 V O and thorium-10-molybdo-2-vanadic acid
  • the preferred bismuth or tellurium containing compounds are the salts of organic or inorganic acids containing either of these elements.
  • the compound is soluble in at least one of the following solvents: water, alcohols, ethers and esters.
  • the preferred catalysts for use in the process of the invention may be represented by the following two general formulae:
  • Me AD O in which Me is bismuth or tellurium
  • x is a number between about 0.2 and about 18;
  • A is cerium or thorium
  • D is tungsten or molybdenum
  • y is a number which depends on the value of x and the valency of the salifying element Me, and usually has a value between about 38 and about 74 and MG AMO V O in which Me is bismuth or tellurium; x is a number between about 0.2 and about 18; A is cerium or thorium; and y is a number between about 37 and about 73.
  • the catalysts may be used either" by themselves or mixed with each other. They may also be used in admixture with a suitable support. Furthermore, they are effective when used both as a fixed and as a fluid bed.
  • the process according to the invention is particularly suitable for the preparation of unsaturated aldehydes from aliphatic olefins having straight or branched chains and containing at least three carbon atoms and at least one methyl group in an alpha-position with respect to the olefinic double bond.
  • the process is particularly effective and gives excellent yields when propylene is used for obtaining acrolein, and isobutene for methacrolein.
  • the olefin may be used in the pure state; however, it has been found that the reaction proceeds equally well when the olefins are diluted with parafiinic hydrocarbons which do not react under the conditions of the process and which behave to all intents and purposes as inert diluents.
  • the oxygen necessary for the reaction may be supplied either in the pure state or in the form of gases, such as, for example, air, containing it.
  • gases such as, for example, air
  • Air in some cases has an advantage in that the nitrogen serves as a diluent and thereby assists in controlling the reaction which is exothermic.
  • diluents are paraffinic hydrocarbons, e.g., those that are found already mixed with the raw olefin used, nitrogen, carbon dioxide, steam, etc.
  • diluent to be used in any given case depends on a number of factors such as the reaction conditions; the degree of conversion obtained and thereby the quantity of heat developed; the selectivity, in order to minimize accompanying side reactions which, being more exothermic than the main reaction, require greater quantities of diluent for the thermal control of the process; and the techniques used, that is to say whether the reaction is effected on a fixed or fluid bed, as well as on the equipment involved.
  • the catalysts used in the process of the invention exhibit very high selectivity so that highly exothermic side reactions are inhibited and the quantit of supplementary diluent in the feed need not be very great and in some cases may even be omitted altogether, especially when air is used to supply the oxygen.
  • the quantity of oxygen, or of the gas containing it, used in relation to the quantity of employed olefin may vary within wide limits.
  • the molar ratio between the oxygen and the olefin is between 0.5 and 2.5.
  • Some gaseous mixtures of olefin and oxygen of certain specific compositions may behave as explosive mixtures. However, the process according to this invention may be carried out even when these circumstances exist.
  • reaction is generally effected with excellent results under atmospheric pressure, it can also be performed at superatmospheric pressures.
  • the invention is preferably carried out at temperatures ranging from about 300 C. to 600 C. However, temperatures in the range between 400 C. and 550 C. are partially preferred because at such temperatures the reaction rate is so high that appreciable conversion rates are attained also by relatively short contact times.
  • the contact time (expressed as the time during which unit volume of the gaseous feed mixture, measured under the average conditions of temperature and pressure existing in the reactor, comes into contact with an apparent unit volume of catalyst) may vary within a wide range, for instance from 0.05 to 20 seconds, but, it has been found that, owing to the high activity of the catalysts, contact times shorter than 1 second are sufficient for obtaining a high conversion, and the preferred contact time is between about 0.1 and about 3 seconds.
  • the heteropolycompounds used as catalysts in the process according to the invention may be prepared in the following way. First the free heteropolyacid or its ammonium salt is prepared by following the general methods described in the literature for their preparation. This heteropolyacid, or its ammonium salt, is then reacted with a compound of the desired salifying element in a liquid reaction medium and in the presence of small quantities of a strong acid.
  • the two reactants that is the heteropolyacid, or the ammonium heteropolysalt, and the compound containing the salifying element, are reacted in stoichiometric amounts in order to obtain as the reaction product the heteropoly salt of the desired element; it is, however, also possible to use an excess or a deficiency with respect to the theoretical value of the compound of the salifying element.
  • the reaction may be effected between the solution or the suspension in suitable solvents of the two reactants.
  • suitable solvent is water, though other solvents, and particularly organic solvents such as alcohols, ethers and esters, may also be used.
  • the reaction is effected in the presence of strong mineral acids; in particular, nitric acid.
  • the conditions at which the reaction is carried out are not critical for obtaining catalysts usable in the process according to the invention.
  • the compound containing the salifying element with the ammonium heteropolysalt in the same reaction medium in which the heteropolysalt has been obtained. This is carried out by mixing first the solution of a salt or of an acid containing the co-ordinated elements with a solution of an acid or a salt containing the coordinating element, and by then adding to the mixture thus obtained the solution of a compound of the salifying element.
  • the product of the catalyst-preparation reaction is evaporated to dryness, for instance by heating it up to C., and, preferably, is subsequently activated by a heat treatment at a temperature lying between 400 C. and 600 C. for a period from 5 to 20 hrs.
  • the activation temperature should be equal to or higher than the temperature at which the catalyst will be operating.
  • the catalysts may be given a particular shape and/ or size by any of the usual methods of grinding, sieving, pressing into tablets, and so on.
  • the drying is stopped when the catalyst has reached a pasty consistency.
  • the mass is then extruded in order to obtain a more homogeneous substance, and is finally activated by heat treatment as described above.
  • a further alternative method of preparation consists in drying the catalyst by a spray-drying system.
  • the product obtained is in a form particularly suitable for use as a fluid bed.
  • the catalyst may be used Without any support or carrier, it is preferred that a support or carrier be used as the effectiveness and the life of the catalyst are thereby enhanced.
  • Suitable substances for this purpose include silica, alumina, Alundum, refractory earths, or the like, which may be in the form of powders, tablets, pellets, granules, or in the form of a gel such as silica or alumina gel.
  • supports which have proved particularly convenient are those which show a so-called open structure, for instance the silica aerogels.
  • open structure for instance the silica aerogels.
  • the techniques most suitable for depositing the catalysts on the supports are well known in the art.
  • the process of the invention has considerable advantages compared to the known processes for the preparation of unsaturated aldehydes.
  • it has been found that it is possible to obtain a high degree of conversion of the olefin without reducing the yield of the unsaturated aldehyde obtained from the reaction.
  • a further important advantage lies in the high degree of selectivity shown by the catalysts used.
  • selectivity is used to indicate that side reactions take place only to a comparatively small extent and that, therefore, only small quantities of byproducts and carbon oxides are formed.
  • the absence of side reactions, which are highly exothermic makes the thermal control of the process a relatively simple matter, thus avoiding special measures for dissipating the intense reaction heats. It will be readily understood by those skilled in the art that this is of considerable practical importance.
  • the mixture obtained is evaporated until dry by heating to 110 C. for 14 hrs., and is then activated in a mufile furnace at 540 C. for 12 hrs.
  • the catalysts thus prepared are suitably subdivided and utilized in a fluid-bed reactor through which a gaseous mixture containing 13.5% propylene, 67.4% air and 19.1% water is passed.
  • the mixture obtained is evaporated by dryness by heating to 110 C. and the mass of catalyst obtained is then activated by prolonged heating at 470 C. After suitable subdivision the catalyst is employed at a fluid bed in a reactor through which a gaseous mixture of 12.4% propylene, 61.8% air and 25.8% steam is fed.
  • Contact time is 0.8 second; temperature is kept constant at 437 C.
  • EXAMPLE 3 A gaseous mixture made up of 7.8% isobutene, 58.7% air, 33.5% steam is passed over the catalyst described in Example 2. Contact time is 0.6 second; the temperature is 438 C.
  • Methacrolein yield is 67.5% of the converted isobutene, which latter represents 40% of the isobutene feed.
  • 29.3 g. of ceric-ammonium nitrate and 170 g. of ammonium tungstate are dissolved in 260 ml. of water.
  • a solution of 234 g. of bismuth nitrate acidified with 26 ml. of nitric acid and 30 g. of a silica aerogel are then added.
  • the mixture obtained is brought to a consistency suitable for extrusion, and is then extruded and dried at 110 C. for 1218 hrs.
  • the dried mass is next activated at 540 C. for 12-18 hrs.
  • the thus prepared catalyst after subdivision suitable for employment in a fluid bed, is placed in a reactor and a gaseous mixture is passed therethrough at constant temperature of 522 C., said mixture being formed of propylene, air and steam as diluent in the proportion of 9.6%, 59.7% and 30.7% respectively.
  • the contact time of this mixture with the catalyst is 0.18 second.
  • Acrolein yield with respect to fed-in propylene is 13.1%
  • the ethereal solution of the heterotriacid obtained is taken again with water and is then evaporated until crystallization begins.
  • the product obtained has the formula H8 1o 2 41)
  • 0.1 mole of this latter, dissolved in water are added to 129 g. of bismuth nitrate dissolved in water acidified with nitric acid; 26.5 g. of silica aerogel (as carrier) are then added.
  • the mass obtained is brought to dryness by heating it to C. and is then activated at 540 C. for 12 hrs.
  • Acrolein yield is 64% with respect to the converted propylene. 17.8% of the propylene feed is transformed to carbon oxides.
  • a catalyst of tellurium ceric molybdovanadate is prepared as follows:
  • the free ceric-molybdovanadic acid is first prepared as set forth in Example 5.
  • the acid is then salified with tellurium by adding to an aqueous solution of 0.1 mole of free heterotriacid the solution obtained by attacking with I-INO 25.5 g. of metallic tellurium.
  • 210 g. of silica aerogel (as a carrier) are then added.
  • the mass obtained is brought to dryness by heating it to 110 C. and is then activated by heating at 490 C. for 12 hrs.
  • a gaseous mixture comprising 12.5% propylene, 62.5 air and 25% steam is passed over the subdivided catalyst placed in a reactor as a fluid bed.
  • Contact time of said mixture with the catalyst is 0.85 second; temperature is kept constant at 373 C.
  • Acrolein yield is 61.4 with respect to the converted propylene.
  • the free heterotriacid is first prepared by operating in a manner analogous to that described in Example 5 for the preparation of ceric-molybdovanadic acid, with, of course,
  • aqueous solution of 0.1 mole of the prepared free thoriomolybdovanadic acid is added to a solution (acidified with nitric acid) of 129 g. of bismuth nitrate, and 250 g. of a silica aerogel are poured onto the resulting mixture. The whole is then dried by heating to 110 C., and is then activated by heating at 540 C. for 8-12 hrs.
  • a similar catalyst may be obtained which contains an excess of the salifying element bismuth with respect to the heteropolyacid, by operating in a similar way and employing 436 g. of bismuth nitrate, rather than 129 as stated above, and 43 g. of silica aerogel.
  • a catalytic system comprising at least one heteropolycompound having as a co-ordinating element lanthanium may be employed, with equally good yields, under suitable conditions.
  • a process for producing acrolein or methacrolein from propylene or isobutylene olefin reactants, respectively, comprising the step of passing a gaseous mixture of oxygen and at least one of said olefin reactants in a molar ratio between 0.5 and 2.5 over a catalyst system consisting essentially of the tellurium salt of at least one heteropolyacid having cerium as the coordinating element selected from the group which consists of the compounds of formulas Te CeM O and Te CeMo V Q at a 8 temperature of between 400 C. and 550 C. with a catalyst-contact time of about 0.1 second to 3 seconds.
  • tellurium salt has the formula 3.
  • tellurium salt has the formula TEgCGMO 10V2041 4.
  • catalyst system is deposited on a silica or alumina support.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US319534A 1962-10-31 1963-10-28 Catalytic process for preparing unsaturated aldehydes Expired - Lifetime US3410910A (en)

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GB (1) GB1037818A (enrdf_load_stackoverflow)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4435397A (en) 1980-04-08 1984-03-06 Nippon Shinyaku Co., Ltd. Carbamylpiperazine compounds

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2373942A (en) * 1942-01-05 1945-04-17 Shell Dev Catalytic hydroxylation of olefinic double bonds
US2744928A (en) * 1952-11-28 1956-05-08 Shell Dev Oxidation of unsaturated aldehydes to acids
US2941007A (en) * 1957-06-10 1960-06-14 Standard Oil Co Process for the oxidation of olefins
GB839808A (en) * 1957-06-21 1960-06-29 Bayer Ag Process for the production of acrolein
BE605502A (fr) * 1960-07-01 1961-11-16 Edison Dept Chimie Procédé pour la production de composés oxygénés per oxydation catalytique directe des oléfines inférieures
US3168572A (en) * 1961-10-06 1965-02-02 Shell Oil Co Production of alpha, beta-unsaturated carbonylic compounds
US3173957A (en) * 1961-08-21 1965-03-16 Eastman Kodak Co Process for the preparation of acrolein

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2373942A (en) * 1942-01-05 1945-04-17 Shell Dev Catalytic hydroxylation of olefinic double bonds
US2744928A (en) * 1952-11-28 1956-05-08 Shell Dev Oxidation of unsaturated aldehydes to acids
US2941007A (en) * 1957-06-10 1960-06-14 Standard Oil Co Process for the oxidation of olefins
GB839808A (en) * 1957-06-21 1960-06-29 Bayer Ag Process for the production of acrolein
BE605502A (fr) * 1960-07-01 1961-11-16 Edison Dept Chimie Procédé pour la production de composés oxygénés per oxydation catalytique directe des oléfines inférieures
US3173957A (en) * 1961-08-21 1965-03-16 Eastman Kodak Co Process for the preparation of acrolein
US3168572A (en) * 1961-10-06 1965-02-02 Shell Oil Co Production of alpha, beta-unsaturated carbonylic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4435397A (en) 1980-04-08 1984-03-06 Nippon Shinyaku Co., Ltd. Carbamylpiperazine compounds

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GB1037818A (en) 1966-08-03
NL143894B (nl) 1974-11-15

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